Process for producing furylpropargylcarbinol and derivative thereof

ABSTRACT

A process for producing furylpropargylcarbinol or a derivative thereof represented by the formula (I): ##STR1## wherein R 1  represents hydrogen or methyl, wherein comprises subjecting a haloallylfurylcarbinol or a derivative thereof represented by the formula (II): ##STR2## wherein R 1  represents a hydrogen or methyl and R 2  represents chlorine, bromine or iodine, to a dehydrohalogenation reaction with a base in a reaction solvent. Furylpropargylcarbinol and a derivative thereof produced according to the process of the present invention are very important as intermediates of agricultural chemicals, perfumes and medicines, and particularly applicable to intermediates of prallethrin.

This is a division of application Ser. No. 07/628,101, filed Dec. 17,1990, now U.S. Pat. No. 5,189,186 which in turn is acontinuation-in-part of application Ser. No. 07/543,541, filed Jun. 26,1990, now abandoned, which in turn is a continuation-in-part ofapplication Ser. No. 07/362,107, filed Jun. 6, 1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Industry

The present invention relates to a process for producingfurylpropargylcarbinol or a derivative thereof represented by theformula (I): ##STR3## wherein R¹ represents a hydrogen atom or a methylgroup.

The furylpropargylcarbinol and a derivative thereof are very importantas intermediates of agricultural chemicals, perfumes and medicines, andparticularly applicable to an intermediate of prallethrin.

2. Description of the Prior Art

As a process for producing furylpropargylcarbinol or a derivativethereof, there has heretofore been a known process using the Grignardreaction of propargyl bromide or propargyl chloride with a furfural-typecompound (Japanese Patent Application Kokai No. 59-118780 ).

Since, however, propargyl bromide and propargyl chloride are detonableor capable of monopropellant-type burning, in view of safety, theinhibition of the detonability is required in the industrial bulk use ofthem. Therefore, the above-mentioned process is not always anindustrially advantageous one.

SUMMARY OF THE INVENTION

The present inventors have found a process for producingfurylpropargylcarbinol or a derivative thereof represented by theformula (I), using neither propargyl bromide nor propargyl chloride.

The present invention relates to a process for producingfurylpropargylcarbinol or a derivative thereof represented by theformula (I) which comprises subjecting a haloallylfurylcarbinol or aderivative thereof represented by the formula (II): ##STR4## wherein R¹represents a hydrogen atom or a methyl group and R² represents achlorine atom, a bromine atom or an iodine atom, to adehydrohalogenation reaction using a base in a solvent.

An object of the present invention is to provide a process for producingfurylpropargylcarbinol and derivatives thereof being important asintermediates of agricultural chemicals, prefumes and medicines, andparticularly applicable as intermediates of prallethrin.

Another object of the present invention is to provide a novelhaloallylfurylcarbinol or a derivative thereof represented by theformula (II).

Further object of the invention is to provide a secure and industriallyadvantageous process for producing furylpropargylcarbinol andderivatives thereof or haloallylfurylcarbinols and derivatives thereofwithout using detonable propargyl chloride or propargyl bromide.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The base used in a dehydrohalogenation reaction according to the presentinvention includes alkali metal hydroxides such as sodium hydroxide,potassium hydroxide, lithium hydroxide and the like; alkali metalalkoxides such as sodium methoxide, sodium ethoxide, sodiumtert-butoxide, potassium methoxide, potassium ethoxide, potassiumtert-butoxide, lithium methoxide, lithium ethoxide, lithium isopropoxideand the like. Preferred examples of the alkali metal hydroxide aresodium hydroxide and potassium hydroxide. Preferred examples of thealkali metal alkoxide are sodium methoxide, sodium ethoxide, potassiummethoxide, potassium ethoxide and potassium tert-butoxide.

The used amount of the base is usually 1-15 parts by mole, preferably1-10 parts by mole for 1 part by mole of haloallylfurylcarbinol or thederivative thereof (II).

To the reaction system can be added a diamine. The diamine includesvarious ones, and however, are preferably aliphatic 1,2- or 1,3-diaminessuch as 1,2-diaminopropane, 1,3-diaminopropane, ethylenediamine,N,N,N',N'-tetramethylethylenediamine, 2,3-diaminobutane,1,3-diaminobutane and the like; and non-aromatic 1,2- or 1,3-diaminessuch as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane,1,8-diazabicyclo[5.4.0]-undec-7-ene and the like. More preferredexamples of the aliphatic 1,2- or 1,3-diamine are 1,2-diaminopropane,1,3-diaminopropane, ethylenediamine,N,N,N',N'-tetramethylethylenediamine.

The used amount of the diamine is usually 1-20 parts by mole, preferably1-15 parts by mole for 1 part by mole of the used haloallylfurylcarbinolor the derivative thereof (II).

The type of reaction solvent used in this reaction depends upon the typeof the used base.

When the alkali metal hydroxide or alkali metal alkoxide is used as thebase, there is used as the reaction solvent, alone or in admixture, apolar aprotic solvent such as acetonitrile, dimethylsulfoxide,N,N-dimethylformamide, N-methyl-2-pyrrolidinone and the like. When thediamine is liquid at room temperature, it can be also used as thereaction solvent, alone or in admixture with other diamine. Examples ofthe diamine are 1,2-diaminopropane, 1,3-diaminopropane, ethylenediamine,N,N,N',N'-tetramethylethylenediamine, 1,5-diazabicyclo[4.3.0]undec-7-eneand non-5-ene, 1,8-diazabicyclo[5.4.0] the like. Usually, the watercontent of the diamine is not more than 10% by weight, preferably notmore than 5% by weight.

When the alkali metal hydroxide is used as the base, if necessary, therecan be also used as the reaction solvent, water and/or an organicsolvent. The organic solvent includes hydrophobic hydrocarbons such astoluene, xylene, pentane, hexane and the like; hydrophobic halogenatedhydrocarbons such as monochlorobenzene, dichlorobenzene and the like;hydrophobic or hydrophilic ethers such as tetrahydrofuran, dioxane,diethyl ether, diglyme and the like. Preferably, the hydrophobichydrocarbons are used. These organic solvents can be used alone or inadmixture.

The used amount of the organic solvent is not particularly critical, andhowever, is usually 0.1-20 parts by weight for 1 part by weight of theused haloallylfurylcarbinol or the derivatives thereof (II). The usedamount of water is 1-4 parts by weight for 1 part by weight of the usedalkali metal hydroxide.

When the alkali metal hydroxide is used as the base, the reaction can bealso carried out without any solvent.

Reaction temperature is usually selected in a range of 0° C.-120° C.,preferably 0° C.-80° C., depending upon the combination of a base and anorganic solvent.

Reaction time is not particularly critical. The end point of thereaction can be determined by following the rate of disappearance of thehaloallylfurylcarbinol or the derivative thereof (II) used as a startingmaterial.

To the reaction system, if necessary, can be added a phase transfercatalyst.

The reaction time can be shortened by the addition of a phase transfercatalyst.

The used amount thereof is usually 0.001-5 parts by mole for 1 part bymole of the used haloallylfurylcarbinol or the derivative thereof (II).

The phase transfer catalyst includes organic quaternary ammonium saltssuch as tetra-n-butylammonium bromide, tetra-n-butylammonium chloride,tetra-n-butylammonium hydrogen sulfate, tetra-n-pentylammonium bromide,tetra-n-pentylammonium iodide, benzyltrimethylammonium chloride,benzyltrimethylammonium bromide, benzyltriethylammonium chloride,benzyltriethylammonium bromide, benzyltripropylammonium chloride,benzyltripropylammonium iodide, cetyltrimethylammonium chloride,1-dodecylpyridinium chloride, 1-hexadecylpyridinium chloride,1-dodecylpyridinium bromide, 1-hexadecylpyridinium bromide and the like;organic quaternary phosphonium salts such as tetraphenylphosphoniumchloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide,benzyltriphenylphosphonium chloride and the like; macrocyclic etherssuch as 18-crown-6, 15-crown-5, 12-crown-4 and the like; polyethyleneglycols of various molecular weights such as polyethylene glycol 200,polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol600 and the like.

After the dehydrohalogenation reaction is completed, thefurylpropargylcarbinol or the derivative thereof (I) can be obtainedfrom the reaction mixture by, for example, the pouring of water,extraction, separation and the like followed by the distillation of anorganic phase.

The haloallylfurylcarbinol or the derivative thereof (II) as a startingmaterial of a process according to the present invention can be producedby reacting, in the presence of zinc in a solvent, furfural or aderivative thereof represented by the formula (III): ##STR5## wherein R¹represents a hydrogen atom or a methyl group, with an organic dihalidecompound represented by the formula (IV): ##STR6## wherein each of X andR² individually represents a chlorine atom, a bromine atom or an iodineatom. Hereinafter, the reaction of furfural or a derivative thereof(III) with an organic dihalide compound (IV) is referred to as thehaloallylfurylcarbinol-producing reaction.

The organic dihalide compound (IV) includes 2,3-dichloro-1-propene,2,3-dibromo-1-propene, 2,3-diiodo-1-propene, 2-chloro-3-bromo-1-propene,2-chloro-3-iodo-1-propene, 2-bromo-3-chloro-1-propene,2-bromo-3-iodo-1-propene, 2-iodo-3-chloro-1-propene,2-iodo-3-bromo-1-propene and the like.

The used amount of the organic dihalide compound (IV) is usually 1-3parts by mole for 1 part by mole of furfural or a derivative thereof(III).

Zinc having various shapes on the market can be used. Zinc powder orzinc particles are preferably used. More preferably, zinc powder isused.

The used amount of zinc is 0.8-3 parts by mole, preferably 1.1-1.5 partsby mole for 1 part by mole of furfural or a derivative thereof (III).

There are used, if necessary, halogenated ammoniums such as ammoniumchloride, ammonium bromide, ammonium iodide and the like. The usedamount thereof is 0.15-6 parts by mole for 1 part by mole of furfural ora derivative thereof (III).

As the solvent of the haloallylfurylcarbinol-producing reaction, thereis used water alone or a mixture of water and an organic solvent. Theorganic solvent includes tetrahydrofuran, dioxane, diglyme, toluene,benzene, monochlorobenzene, ethylene dichloride, polar aprotic solventssuch as acetonitrile, dimethylsulfoxide, N,N-dimethylformamide, N-methyl2-pyrrolidinone, etc., and the like.

When the solvent is a mixture, the solvent should contain water as amain component. The water content of the mixture is preferably 50% byweight or more.

The amount of water in the solvent is usually 3-24 parts by weight,preferably 4-19 parts by weight for 1 part by weight of furfural or aderivative thereof (III).

To the haloallylfurylcarbinol-producing reaction, if necessary, can beadded a phase transfer catalyst. The used amount thereof is usually0.05-0.4 parts by weight for 1 part by weight of furfural or aderivative thereof (III).

The phase transfer catalyst includes the above-mentioned organicquaternary ammonium salts.

A reaction temperature of the haloallylfurylcarbinol-producing reactionis in a range of 0° C.-100° C., preferably 15° C.-50° C.

Reaction time of the haloallylfurylcarbinol-producing reaction isusually 1-8 hours and, however, it can be shortened by the addition of asmall amount of an acid.

The acid includes acetic acid, hydrochloric acid, sulfuric acid and thelike.

When acetic acid is used as the acid, the added amount thereof ispreferably 5% by weight or less based on the water contained in thesolvent. When hydrochloric acid or sulfuric acid is used as the acid,the added amount thereof is preferably 0.1% by weight based on the watercontained in the solvent.

After the haloallylfurylcarbinol-producing reaction is completed, thehaloallylfurylcarbinol or the derivative thereof (II) can be obtainedfrom the reaction mixture by, for example, filtration, separationfollowed by the distillation of an organic phase or by columnchromatography.

Thus, according to the process of the present invention,furylpropargylcarbinol and derivatives thereof represented by theformula (I) can be produced in safety and industrially with advance.

The present invention is explained more specifically below referring toExamples and Referential Examples. However, the present invention shouldnot be construed to be restricted by the Examples.

REFERENTIAL EXAMPLE 1

Into a reactor were charged 380 g of 30%-aqueous sodium hydroxide and2.4 g of 68%-aqueous solution of benzyltriethylammonium chloride and themixture was stirred at 20°-30° C. for 30 minutes. The mixture was cooleddown to 10° C., and thereinto, 340 g of 30%-aqueous sodium hydroxide and340 g of crude 1,2,3-trichloropropane having a purity of 73% weredropped together at 10°-15° C. in 25 minutes. The mixture was stirred at10°-15° C. for 90 minutes, and thereafter, 300 g of water was addedthereto. The resulting mixture was subjected to separation to obtain 248g of an organic phase.

The content of 2,3-dichloro-1-propene in the organic phase was 71.7% byweight (yield: 95.2%), the content of 1,2,3-trichloropropane was 0.2% byweight or less.

The organic phase was subjected to simple distillation to obtain 170 gof 2,3-dichloro-1-propene having a purity of 93.8%.

EXAMPLE 1

(1) Into a reactor were charged 20.0 g of 5-methyl-furfural, 88 g ofwater, 33 g of toluene and 26 g of zinc powder and the mixture was keptat 33°-35° C. Thereinto, 44.4 g of distilled 2,3-dichloro-1-propeneobtained in Referential Example 1 was dropped in 20 minutes. Thereaction mixture was kept at 33°-35° C. for 4 hours. After the reactionwas completed, the crystals derived from the zinc powder were filteredoff. To the filtrate was added 66 g of toluene and a toluene phase wasseparated. The toluene phase was washed with 30 g of 7%-aqueous sodiumcarbonate and subsequently with 50 g of water, and thereafter, toluenewas distilled off at 60° C. or less. The resulting residue was subjectedto simple distillation to obtain 30.5 g of2'-chloroallyl-5-methylfurylcarbinol.

Boiling point : 84°-85° C./0.8 mmHg.

Yield : 90%.

¹ H-NMR data (measurement solvent : CDCl₃, internal standard : TMS,chemical shift : δ-value): 2.27 (s, 3H), 2.75-2.92 (m, 2H), 4.95 (dd,1H), 5.25 and 5.26 (s, 2H), 5.89 (d, 1H) and 6.13 (d, 1H).

(2) The mixture of 12.3 g of 2'-chloroallyl-5-methylfurylcarbinolobtained in (1), 42.3 g of 50%-aqueous sodium hydroxide, 37 g of tolueneand 15.1 g of benzyl-triethylammonium chloride was stirred at 40° C. for8 hours. To the mixture were added 100 g of toluene and 100 g of water,and extraction and separation were carried out. The organic phase waswashed with 5%-aqueous hydrochloric acid and subsequently with7%-aqueous sodium carbonate, and thereafter, the organic phase wasconcentrated under a reduced pressure.

The resulting residue was subjected to simple distillation to obtain7.86 g of 5-methylfurylpropargylcarbinol.

Boiling point : 74° C./0.7 mmHg.

Yield : 79.2%

¹ H-NMR data (measurement solvent : CDCl₃, internal standard: TMS,chemical shift: δ-value) : 2.03 (t, 1H, J=2.6 Hz), 2.25 (d, 3H, J=1.0Hz), 2.70 (dd, 2H, J=6.6 Hz, 2.6 Hz), 2.89 (brs, 1H), 4.76 (t, 1H, J=6.6Hz), 5.86 (dq, 1H, J=3.3 Hz, 10 Hz) and 6.17 (d, 1H, J=3.3 Hz).

EXAMPLE 2

The mixture of 12.3 g of 2'-chloroallyl-5-methylfurylcarbinol, 42.3 g of50%-aqueous sodium hydroxide, 37 g of toluene and 21.3 g oftetra-n-butylammonium bromide was stirred at 40° C. for 8 hours.Thereafter, the same procedure was repeated as in Example 1 (2) toobtain 7.94 g of 5-methylfurylpropargylcarbinol (yield: 80.0%).

EXAMPLE 3

The mixture of 20.0 g of 2'-chloroallylfurylcarbinol, 97.4 g of40%-aqueous potassium hydroxide, 40 g of hexane and 28.1 g oftrioctylmethylammonium bromide was stirred at room temperature for 24hours. Thereafter, the same procedure was repeated as in Example 1 (2)to obtain 13.0 g of furylpropargylcarbinol (yield: 82.3%).

EXAMPLE 4

18.66 g of 2'-chloroallyl-5-methylfurylcarbinol was dissolved in 18.66 gof toluene. To the solution was added 64.00 g of 50%-aqueous sodiumhydroxide and 20.00 g of polyethylene glycol 200. The reaction mixturewas kept at 40° C. for 24 hours. To the mixture, toluene and water wereadded, followed by extraction. The organic phase was separated, washedwith 7%-aqueous sodium carbonate, and thereafter, the organic phase wasconcentrated under a reduced pressure. The resulting residue wassubjected to simple distillation to obtain 13.35 g of5-methylfurylpropargylcarbinol (yield 88.9%).

EXAMPLE 5

Into the mixture of 22.0 g of 5-methylfurfural, 265 g of 12.5%-aqueousammonium chloride, 2.6 g of tetrabutylammonium bromide, 33 g of tolueneand 26 g of zinc powder, 44.4 g of 2,3-dichloro-1-propene was dropped at33°-35° C. in an hour. The reaction mixture was stirred at the sametemperature for 3 hours. After the reaction was completed, the crystalsderived from the zinc powder was filtered off and 66 g of toluene wasadded to the filtrate. A toluene phase was separated and washed with 60g of 15%-aqueous sodium bisulfite and subsequently with 50 g of water,and thereafter, toluene was removed at 60° C. or less. The resultingconcentrated residue was subjected to simple distillation to obtain 32.0g of 2'-chloroallyl-5-methylfurylcarbinol.

Boiling point: 84°-85° C./0.8 mmHg.

Yield: 85%.

10.0 g of 2'-chloroallyl-5-methylfurylcarbinol was dissolved in 100 g ofN,N-dimethylformamide. To the solution was added 6.43 g of sodiumhydroxide. The reaction mixture was kept at 40° C. for 3 hours. Themixture was neutralized with 10%-aqueous hydrochloric acid, andthereafter, the solvent was distilled off under a reduced pressure. Theresulting residue was added to a mixture of toluene and water. Theorganic phase was separated and thereafter concentrated under a reducedpressure. Thereafter, the organic phase was purified by distillation toobtain 6.92 g of 5-methylfurylpropargylcarbinol (yield : 86.0%).

EXAMPLE 6

The mixture of 18 g of furfural, 33 g of toluene, 88 g of 3%-aqueousacetic acid and 26 g of zinc powder was kept at 33°-35° C. withstirring.

44.4 g of 2,3-dichloro-1-propene was dropped thereinto at the sametemperature in 20 minutes, and thereafter, the reaction mixture was keptat the same temperature for 2 hours. After the reaction was completedthe crystals derived from zinc powder was filtered off. To the filtratewas added 66 g of toluene, and the toluene phase was separated. Thetoluene phase was washed with 30 g of 7%-aqueous sodium carbonate andsubsequently with 50 g of water. Thereafter, toluene was removed at 60°C. or less. The resulting residue was subjected to simple distillationto obtain 29.4 g of 2'-chloroallylfurylcarbinol.

Boiling point: 74° C./0.7 mmHg.

Yield 91.0%.

¹ H-NMR data (measurement solvent : CDCl₃, internal standard: TMS,chemical shift: δ-value) : 2.68 (d, 1H, J=4.3 Hz), 2.83 (m, 2H), 5.00(m, 1H), 5.24 (m, 2H), 6.25 (dd, 1H, J=3.3, 0.7 Hz), 6.32 (dd, 1H, J=3.3, 2.0 Hz), 7.36 (dd, 1H, J=2.0, 0.7 Hz).

EXAMPLE 7

Into the mixture of 11.0 g of 5-methylfurfural, 38.4 g of 3%-aqueousacetic acid, 43.2 g of toluene and 13.1 g of zinc powder, 40.0 g of2,3-dibromo-1-propene was dropped at 30°-35° C. in 20 minutes. After thedropping was completed, the reacting mixture was stirred at 30°-35° C.for 2 hours. After the reaction was completed, the crystals derived fromthe zinc powder were filtered off and the obtained crystals were washedwith 86 g of toluene. The filtrate and the wash liquid were combined toobtain a filtrate mixture. The toluene phase was separated from thefiltrate mixture. The toluene phase was washed with 30 g of 7%-aqueoussodium carbonate and subsequently with 50 g of water. Thereafter,toluene was removed at 60° C. or less. The resulting residue waspurified by column chromatography using 100 g of silica gel as a packingand ethyl acetate as an eluent. Thereby, 11.1 g of2'-bromoallyl-5-methylfurylcarbinol was obtained.

Yield: 48.2%.

FD-Mass spectrum data: M⁺ 230, M⁺ +2 232 .

¹ H-NMR data (measurement solvent: CDCl₃ internal standard: TMS,chemical shift: δ-value): 2.08 (brs, 1H), 2.28 (d, 3H, J=1.0 Hz), 2.93(m, 2H), 4.98 (dd, 1H, J=5.1 Hz, 8.4 Hz), 5.54 (d, 1H, J=1.7 Hz), 5.72(d, 1H, J=1.7 Hz), 5.91 (m, 1H), 6.16 (d, 1H, J=3.3 Hz).

IR data: 3380 cm⁻¹ (O--H, stretching vibration), 1620 cm⁻¹ (vinylideneC═C, stretching vibration).

EXAMPLE 8

18.4 g of 2'-chloroallyl-5-methylfurylcarbinol was dissolved in 88.8 gof ethylenediamine. The solution was cooled to 10° C. To the solutionwas added 7.88 g of flaky sodium hydroxide. The reaction mixture waskept at 10° C. for 24 hours. The mixture was neutralized with aceticacid, and thereafter, undissolved cake contained in the solution werefiltered off. The filtrate was concentrated under a reduced pressure.The resulting residue was subjected to simple distillation to obtain13.66 g of 5-methylfurylpropargylcarbinol (yield 92.3%).

EXAMPLES 9-12

Reaction and post-treatment were carried out in the same manner as inExample 8, except that a haloallylfurylcarbinol or a derivative thereof,a base, a solvent shown in Table 1 were substituted for5-methylchloro-allylfurylcarbinol, sodium hydroxide and ethylenediamine.Results are shown in Table 1.

EXAMPLE 13

10.0 g of 2'-chloroallyl-5-methylfurylcarbinol was dissolved in 100 g ofN-methyl-2-pyrrolidinone. To the solution was added 8.68 g of sodiummethoxide. The reaction mixture was kept at 50° C. for 5 hours. Themixture was neutralized with 10%-aqueous hydrochloric acid, andthereafter the solvent was removed under a reduced pressure. Theresulting residue was purified by distillation to obtain 6.10 g of5-methylfurylpropargylcarbinol (yield : 75.8%).

                                      TABLE 1                                     __________________________________________________________________________    Haloallylfuryl-                              Furylpropargyl-                  carbinol or a deriv-                         carbinol or a deriv-             ative thereof (II) Base         Solvent      ative thereof (I)                Example                                                                            Name of                                                                              Amount used                                                                          Name of                                                                             Amount used                                                                          Name of                                                                             Amount used                                                                          Name of                                                                             Yield                      No.  compound                                                                             (g)    compound                                                                            (g)    compound                                                                            (g)    compound                                                                            (%)                        __________________________________________________________________________     9   2'-chloro-                                                                           18.2   KOH   8.19   ethylene-                                                                           58.6   5-methyl-                                                                           90.2                            allyl-5-                   diamine      furyl-                                methylfuryl-                            propargyl-                            carbinol                                carbinol                         10   2'-chloro-                                                                           18.0   NaOH  6.26   1,3-  77.3   furyl-                                                                              92.1                            allylfuryl-                diamino-     propargyl-                            carbinol                   propane      carbinol                         11   2'-bromo-                                                                            23.5   KOH   8.57   1,3-  37.7   5-methyl-                                                                           89.0                            allyl-5-                   diamino-     furyl-                                methylfuryl-               propane      propargyl                             carbinol                   propane      carbinol                         12   2'-chloro-                                                                           10.0   NaOEt 3.47   ethylene-                                                                           32.2   5-methyl-                                                                           92.3                            allyl-5-                   diamine      furyl-                                methylfuryl-                            propargyl-                            carbinol                                carbinol                         __________________________________________________________________________

EXAMPLE 14

Into the mixture of 9.6 g of furfural, 38.4 g of 3%-aqueous acetic acid,43.2 g of toluene and 13.1 g of zinc powder, 40.0 g of2,3-dibromo-1-propene was dropped at 30°-35° C. in 20 minutes. After thedropping was completed, the reaction mixture was stirred at 30°-35° C.for 2 hours. After the reaction was completed, the crystals derived fromzinc powder were filtered off and the obtained crystals were washed with86 g of toluene. The filtrate and the wash liquid were combined toobtain a filtrate mixture. The toluene phase was separated from thefiltrate mixture. The toluene phase was washed with 30 g of 7%-aqueoussodium carbonate and subsequently with 50 g of water. Toluene wasremoved at 60° C. or less. The resulting residue was purified by columnchromatography using 100 g of silica gel as a packing and ethyl acetateas an eluent. Thereby, 10.2 g of 2'-bromoallylfurylcarbinol wasobtained.

Yield: 47.2%.

FD-Mass spectrum data: M⁺ 216, M⁺ +2 218 .

¹ H-NMR data (measurement solvent: CDCl₃, internal standard: TMS,chemical shift: δ-value): 2.28 (brs, 1H), 2.94 (m, 2H), 5.04 (dd, 1H,J=5.6, 7.9 Hz), 5.54 (d, 1H, J=1.7 Hz), 5.71 (d, 1H, J=1.7 Hz), 6.29 (m,1H), 6.33 (m, 1H), 7.38 (m, 1H).

IR data: 3380 cm³¹ 1 (O--H, stretching vibration), 1630 cm³¹ l(vinylidene C═C, stretching vibration).

The same dehydrohalogenation reaction and post-treatment are repeated asin Example 11, except that the obtained 2-bromoallylfurylcarbinol issubstituted for 2'-chloroallyl-5-methylfurylcarbinol. As a result,furylpropargylcarbinol is obtained.

EXAMPLE 15

Into the mixture of 11.0 g of 5-methylfurfural and 40.0 g of water wasadded each of 22.1 g of 2,3-dichloro-1-propene, 2.3 g of 50%-aqueousacetic acid and 13.1 g of zinc powder at 30°-35° C. in 3 hours. Afterthe addition was completed, the reaction mixture was stirred at 30°-35°C. for 3 hours. After the reaction was completed, the crystals derivedfrom the zinc powder were filtered off and the obtained crystals werewashed with 120 g of toluene. The filtrate and the wash liquid werecombined to obtain a filtrate mixture. The toluene phase was separatedfrom the filtrate mixture. The toluene phase was washed with 30 g of7%-aqueous sodium carbonate and subsequently with 50 g of water. Toluenewas removed at 60° C. or less. The resulting residue was subjected tosimple distillation to obtain 13.2 g of2'-chloroallyl-5-methylfurylcarbinol (yield: 70.5%).

The same dehydrohalogenation reaction and post-treatment were repeatedas in Example 1 (2), using the obtained2'-chloroallyl-5-methylfurylcarbinol. As a result,5-methylfurylpropargylcarbinol was obtained.

EXAMPLE 16

The mixture of 37.33 g of 2'-chloroallyl-5-methylfurylcarbinol, 56.11 gof potassium hydroxide, 112 g of toluene and 1.29 g oftetra-n-butylammonium bromide was stirred at 40° C. for 7 hours.Thereafter, the same procedure was repeated as in Example 1 (2) toobtain 24.70 g of 5-methylfurylpropargylcarbinol (yield: 82.3%).

EXAMPLE 17

The mixture of 37.33 g of 2'-chloroallyl-5-methylfurylcarbinol, 56.11 gof potassium hydroxide, and 112 g of toluene was stirred at 40° C. for10.5 hours. Thereafter, the same procedure was repeated as in Example 1(2) to obtain 24.42 g of 5-methylfurylpropargylcarbinol (yield: 81.3%).

EXAMPLE 18

The mixture of 37.33 g of 2'-chloroallyl-5-methylfurylcarbinol, 56.11 gof potassium hydroxide, 112 g of toluene and 1.36 g oftetra-n-butylphosphonium bromide was stirred at 40° C. for 8 hours.Thereafter, the same procedure was repeated as in Example 1 (2) toobtain 24.06 g of 5-methylfurylpropargylcarbinol (yield: 80.1%)

EXAMPLE 19

The mixture of 37.33 g of 2'-chloroallyl-5-methylfurylcarbinol, 80.00 gof sodium hydroxide, 56.0 g of toluene and 12.89 g oftetra-n-butylammonium bromide was stirred at 50° C. for 7 hours.Thereafter, the same procedure was repeated as in Example 1 (2) toobtain 22.85 g of 5-methylfurylpropargylcarbinol (yield: 76.1%).

EXAMPLE 20

The mixture of 18.67 g of 2'-chloroallyl-5-methylfurylcarbinol, 78.55 gof 50%-aqueous potassium hydroxide, and 16.98 g of tetra-n-butylammoniumhydrogen sulfate was stirred at 50° C. for 7 hours. Thereafter, the sameprocedure was repeated as in Example 1 (2) to obtain 10.51 g of5-methylfurylpropargylcarbinol (yield: 70.0%).

What is claimed is:
 1. A haloallylfurylcarbinol or a derivative thereofrepresented by the formula (II): ##STR7## wherein R¹ represents ahydrogen atom or a methyl group and R² represents chloride, bromine oriodine.
 2. A haloallylfurylcarbinol or a derivative thereof according toclaim 1, wherein R¹ is hydrogen atom R² is chlorine.
 3. Ahaloallylfurylcarbinol or a derivative thereof according to claim 1,wherein R¹ is methyl and R² is chlorine.
 4. A haloallylfurylcarbinol ora derivative thereof according to claim 1, wherein R¹ is hydrogen and R²is bromine.
 5. A haloallylfurylcarbinol or a derivative thereofaccording to claim 1, wherein R¹ is methyl and R² is bromine.
 6. Aprocess for producing a haloallylfurylcarbinol or a derivative thereofrepresented by the formula (II); ##STR8## wherein R¹ represents hydrogenor methyl and R² represents chlorine, bromine or iodine, which comprisesreacting furfural or a derivative thereof represented by the formula(III): ##STR9## wherein R¹ represents hydrogen or methyl, with anorganic dihalide compound represented by the formula (IV): ##STR10##wherein each of R² and X independently represents chlorine, bromine oriodine, in the presence of zinc in a solvent selected from the groupconsisting of water and a mixture of water and an organic solvent.
 7. Aprocess for producing a haloallylfurylcarbinol or a derivative thereofaccording to claim 6, wherein the organic dihalide compound is2,3-dichloro-1-propene or 2,3-dibromo-1-propene.
 8. A process forproducing a haloallylfurylcarbinol or a derivative thereof according toclaim 6, wherein the reaction is carried out in the presence of an acid.9. A process for producing a haloallylfurylcarbinol or a derivativethereof according to claim 8, wherein the organic dihalide compound is2,3-dichloro-1-propene or 2,3-dibromo-1-propene.